EP1052230A1 - Composition de revêtement pour la coloration de verre - Google Patents

Composition de revêtement pour la coloration de verre Download PDF

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Publication number
EP1052230A1
EP1052230A1 EP00108471A EP00108471A EP1052230A1 EP 1052230 A1 EP1052230 A1 EP 1052230A1 EP 00108471 A EP00108471 A EP 00108471A EP 00108471 A EP00108471 A EP 00108471A EP 1052230 A1 EP1052230 A1 EP 1052230A1
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EP
European Patent Office
Prior art keywords
pigment
type pigment
type
coating composition
organic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP00108471A
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German (de)
English (en)
Inventor
Tetsuro Toyo Ink Manuf. Co. Ltd. Oizumi
Naohisa Toyo Ink Manuf. Co. Ltd. Hirota
Toshiyuki Toyo Ink Manuf. Co. Ltd. Hashimoto
Shinichi Toyo Ink Manuf. Co. Ltd. Sato
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Toyo Ink Mfg Co Ltd
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Toyo Ink Mfg Co Ltd
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Publication of EP1052230A1 publication Critical patent/EP1052230A1/fr
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/10Deposition methods
    • C03C2218/11Deposition methods from solutions or suspensions
    • C03C2218/113Deposition methods from solutions or suspensions by sol-gel processes

Definitions

  • the present invention relates to a coloring coating composition for forming a thin film of colored glass gel on the surface of glass for the purpose of recycling colored glass products, and, more particularly, to a coating composition for coloring glass enabling the recycling of colored glass products as non-colored glass by achromatizing the colored glass when it is remelted.
  • glass is an excellent material in order to promote resource savings and to recycle since glass contains, as its major component, silicon dioxide used for various purposes and can be reused by recovering it and remelting it as a cullet.
  • Glass products include non-colored products and colored products.
  • the colored products can be returned to non-colored materials with difficulty by remelting because they contain a variety of transition metals.
  • it is necessary to classify recovered glass products into non-colored glass products and colored glass products or to recover classified glass products from beginning to remelt only non-colored glass products. Much laborious work is needed to obtain non-colored glass in this manner. This reduces the recycling rate of glass.
  • a method for achromatizing colored glass when it is remelted a method in which glass is coated with a thin film of colored glass gel by using a sol-gel method is proposed.
  • glass is coated with a metal alkoxide solution containing an organic dye and is baked to form a thin film of colored glass gel.
  • a metal alkoxide solution containing an organic dye is applied to glass and baked to form a thin film of glass gel (see Japanese Patent Application Laid-Open (JP-A) No. 1-320742).
  • the baking temperature must be 300°C or less on account of the decomposition temperature of the organic dye and hence the resulting thin film of glass becomes a porous one having a greater number of pores, giving rise to a water-resistance problem, namely the problem that a dye is eluted due to the intrusion of water, chemicals and the like from these pores resultantly.
  • this thin film of glass gel is permeable to oxygen and the like, posing the problem that the color of the dye is faded by oxidation, resulting in poor UV-ray characteristics and the like.
  • Glass products circulated in the market, particularly those having high utilization for the color of glass bottles include green glass products.
  • Inorganic pigments are used to reproduce green colors including emerald green, namely yellowish green, produced by blending a trivalent chromium oxide and Georgia green, namely more slightly bluish than the above emerald green, produced by blending a trivalent chromium oxide and a bivalent cobalt oxide.
  • the hue of green color products circulated in the market widely ranges from a yellowish one to a bluish one.
  • Organic pigments such as copper phthalocyanine chloride (C.I. Pigment Green 7) and copper phthalocyanine chlorobromide (C.I. Pigment Green 36) give colors much more bluish than the green color obtained when an inorganic pigment containing a chromium ion is used. Therefore no wide range of hue can be reproduced.
  • a green coating composition for coloring glass comprising a green colorant formed by color-mixing a blue organic pigment and a yellow organic pigment, a silicon alkoxide compound or a metal alkoxide compound ,and an organic resin.
  • the present invention provides a green coating composition for coloring glass wherein the organic resin is at least one type selected from the group consisting of an acrylic resin, a polyvinylacetal resin, a cellulose resin and a urethane resin.
  • the present invention provides the coating composition for coloring glass wherein the blue organic pigment is a phthalocyanine type pigment.
  • the present invention provides the coating composition for coloring glass wherein the yellow organic pigment is at least one type selected from the group consisting of an isoindoline type pigment, an azo type pigment, an isoindolinone type pigment, a quinophthalone type pigment, an anthrapyrimidine type pigment, a flavanthrone type pigment, a perinone type pigment, a benzimidazolone type pigment, a condensed azo type pigment, a methine type pigment, an azomethine type pigment and a metal complex type pigment.
  • the yellow organic pigment is at least one type selected from the group consisting of an isoindoline type pigment, an azo type pigment, an isoindolinone type pigment, a quinophthalone type pigment, an anthrapyrimidine type pigment, a flavanthrone type pigment, a perinone type pigment, a benzimidazolone type pigment, a condensed azo type pigment, a methine type pigment, an azomethine
  • the present invention provides the coating composition for coloring glass comprises a pigment dispersant.
  • the present invention it is possible to obtain a recyclable coloring glass by applying the green coating composition to a glass.
  • the coating composition has high fluidity and storage stability, enables an expression of a wide range of hue, offers no danger of producing harmful substances such as a dioxin when it is incinerated.
  • the coating composition also possesses desired light absorption characteristics in the UV range or the visible range, water resistance, anti-UV-ray characteristics and anti-abrasion characteristics and has excellent glossiness, transparency, clearness and tinting strength.
  • the present disclosure relates to subject matter contained in the Japanese Patent Application No. HEI 11-110253, filed on April 19, 1999, the disclosure of which is expressly incorporated herein by reference in its entirely.
  • the green coating composition for coloring glass according to the present invention comprises a green colorant formed by color-mixing a blue organic pigment and a yellow organic pigment, a silicon alkoxide compound or a metal alkoxide compound, and an organic resin.
  • the blue organic pigment used in the present invention is used for paints or printing inks.
  • the blue organic pigment may include C.I. Pigments Blue 15, 15:1-6, 16 and 60.
  • Particularly C.I. Pigments 15:1-4 are preferable since these pigments are superior in many characteristics such as light resistance.
  • the yellow organic pigment used in the present invention insofar as it is used for paints or printing inks.
  • the yellow organic pigment may include isoindoline type pigments, azo type pigments, isoindolinone type pigments, quinophthalone type pigments, anthrapyrimidine type pigments, flavanthrone type pigments, perinone type pigments, benzimidazolone type pigments, condensed azo type pigments, methine type pigments, azomethine type pigments and metal complex type pigments.
  • Pigment Yellow 129 which is a copper azomethine pigment is advantageous on the premise that the dye is decomposed by incineration, because it is superior in many resistances such as light resistance and alkali resistance and includes no chlorine in the skeleton of the pigment.
  • the green colorant used in the present invention is obtained by compounding the blue organic pigment with the yellow organic pigment.
  • the proportion of the green colorant is preferably 0.01 to 200 parts by weight based on 100 parts by weight of the silicon alkoxide compound or metal alkoxide compound. When the proportion is less than 0.01 parts by weight, sufficient tinting strength cannot be obtained, when the green colorant is used in a proportion exceeding 200 parts by weight, the strength of the resulting thin film decreases.
  • a pigment dispersant may be used if necessary.
  • Materials used for the pigment dispersant include surfactants, resin type dispersants, amine derivatives containing an organic dye residue or heterocycle residue, coupling agents, chelate type dispersants and lecithin or the like. These may be used either singly or in combinations of two or more.
  • Examples of the amine derivatives containing an organic dye residue or heterocycle residue may include compounds represented by the general formulae (1) and (2).
  • P-[X-Y-Z-N(R 1 )R 2 ] n wherein P represents an organic dye residue or a heterocycle residue, X represents a bivalent bond group comprising a reasonable combination constituted of 2-15 atoms selected from S, C, N, O or H, Y represents a direct bond, -N(R)- (where R represents H, an alkyl group having 1-18 carbon atoms or -Z-N(R 1 )R 2 ) or -O-, Z represents an alkylene group having 1-6 carbon atoms, R 1 and R 2 respectively represent an alkyl group having 1-18 carbon atoms which may be substituted or are combined to represent a heterocycle which may contain N, O or S and may be substituted, and n denotes an integer from 1 to 3.
  • T represents -NH 2 , P-X- (where P represents an organic dye residue or a heterocycle residue, X represents a bivalent bond group comprising a reasonable combination constituted of 2-15 atoms selected from S, C, N, O or H), or a compound represented by the general formula(3):
  • Q represents a compound represented by the general formula (4): A represents a hydroxyl group or -N(R)-Z-N(R 1 )R 2 , R represents H, an alkyl group having 1-18 carbon atoms or -Z-N(R 1 )R 2 , Z represents an alkylene group having 1-6 carbon atoms, and R 1 and R 2 respectively represent an alkyl group having 1-18 carbon atoms which may be substituted or are combined to represent a heterocycle which may contain N, O or S and may be substituted.
  • P in the general formulae (1) and (2) represents an organic dye residue or a heterocycle residue.
  • the organic dye residue residual groups such as a phthalocyanine type, insoluble azo type, azo lake type, anthraquinone type, quinacridone type, dioxazine type, diketopyrrolopyrrole type, anthrapyridine type, anthanthrone type, indanthrone type, flavanthrone type, perinone type, perillene type and thioindigo type may be exemplified.
  • organic dye residues may be optionally selected, it is practically advantageous to use an organic dye residue having the same or similar skeleton and hue as the organic pigment used in the coating composition.
  • An organic dye residue having such a structure not only has a high effect on the non-flocculating ability, non-crystallinity, fluidity and the like but also decreases a variation in hue.
  • heterocycle residue may include thiophene, furan, xanthene, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, indole, quinoline, carbazole, acridine, acridone and anthraquinone and the like.
  • P in the formulae (1) or (2) is a heterocycle residue, a non-colored or almost uncolored diamine derivative is obtained.
  • the above residues are preferable in the point that these residues can be used for various purposes.
  • the bond group X in the general formula (1) is a bivalent bond group comprising a reasonable combination constituted of 2-15 atoms selected from S, C, N, O and H.
  • R 1 and R 2 in the general formulae (1) and (2) respectively represent an alkyl group having 1-18 carbon atoms.
  • these alkyl groups lower alkyl groups such as a methyl group, ethyl group, propyl group and butyl group are preferable.
  • the alkyl group may be branched within a range of the number of carbons up to 18 and may be substituted.
  • R 1 and R 2 may be joined with each other to form a five- or six-membered heterocycle containing N, O or S depending on the situation.
  • a method of the production of the compound represented by the general formula (1) is as follows. Firstly, a substituent such as -SO 2 Cl, -COCl, -CH 2 Cl or -CH 2 NHCOCH 2 Cl- is introduced into an organic dye or heterocycle by a well-known method and is reacted with an amine compound having the structure Z-N(R 1 )R 2 corresponding to the general formula (1) to obtain an organic dye derivative represented by the general formula (1).
  • Examples of the amine compound having the structure Z-N(R 1 )R 2 include N,N-dimethylaminomethylamine, N,N-dimethylaminoethylamine, N,N-diethylaxninoethylamine, N,N-dibutylaminoethylamine, N,N-diethylaminopropylamine, N,N-dibutylaminopropylamine, N,N-dimethylaminobutylamine, N,N-diethylaminobutylamine, N,N-dipropylaminobutylamine, N,N-dibutylaminobutylamine, N,N-diethylaminohexylamine, N,N-diisobutylaminopentylamine, N,N-methyl-laurylaminopropylamine, N,N-ethyl-hexylaminoethylamine, N,N-d
  • a method of the production of the compound represented by the general formula (2) is as follows.
  • T in the general formula (2) is P-X-, for example, P is chlorosulfonated according to the usual method, or is chlorinated using thionyl chloride, phosphorous pentachloride or the like if P has a sulfone group or a carboxyl group originally, and thereafter the resulting product is reacted with a compound represented by the following general formula (5), thereby obtaining the object compound.
  • Q, R, R 1 , R 2 and A have the same meanings as above.
  • the compound represented by the general formula (5) can be produced, for instance, by reacting a compound, produced by reacting p-amino-acetanilide and cyanuric chloride at the same molar ratio, with the aforementioned amine compound having the structure Z-N(R 1 )R 2 , and by hydrolyzing the resulting product by using an aqueous hydrochloric acid solution. If one chlorine atom of cyanuric chloride remains unreacted, it is hydrolyzed into a hydroxyl group.
  • the compound represented by the general formula (5) can also be produced by reacting a compound, produced using p-nitro-aniline in place of p-amino-acetanilide, with amines, followed by a reduction of a nitro group.
  • the compound represented by the general formula (2) can also be produced by reacting a compound, produced from diaminodianthraquinone and cyanuric chloride, with the aforementioned amine compound having the structure Z-N(R 1 )R 2 .
  • the organic dye residue- or heterocycle residue-containing amine derivative used in the present invention may be used either in a dry powder form when the organic pigment is dispersed or in the condition that it is mixed in the organic pigment in advance, to obtain a pigment composition.
  • the pigment composition may be obtained by adding the organic dye residue- or heterocycle residue-containing amine derivative to a solution or slurry of a solvent containing the organic pigment to adsorb the amine to the surface of the organic pigment and by drying the resulting product as required after filtration.
  • the pigment composition may also be obtained by a method in which a powder, solution or dispersion of the organic dye residue- or heterocycle residue-containing amine derivative is added, particularly during coupling in the case of using an azo type pigment or during a pigmentation step such as a salt milling process or a sulfuric acid dissolution process in the case of using a phthalocyanine type, quinacridone type or dioxazine type pigment, to adsorb the derivative to the surface of the pigment, followed by drying as required after filtration.
  • a powder, solution or dispersion of the organic dye residue- or heterocycle residue-containing amine derivative is added, particularly during coupling in the case of using an azo type pigment or during a pigmentation step such as a salt milling process or a sulfuric acid dissolution process in the case of using a phthalocyanine type, quinacridone type or dioxazine type pigment, to adsorb the derivative to the surface of the pigment, followed by drying as required after filtration.
  • the resin type dispersant used in the present invention is high molecular copolymerized products produced by combining a basic material with a polyester compound or an acrylic polymer and having a weight average molecular weight of 1,000 to 100,000 and an amine value of 10 to 200 mgKOH/g.
  • These resin type dispersants are disclosed, for example, in JP-A-60-166318, JP-A-61-174939 and JP-A-46-7294.
  • the weight average molecular weight of the high molecular copolymerized product is less than 1,000, only insufficient steric hindrance is obtained, reducing the dispersing effect.
  • the weight average molecular weight exceeds 100,000, this effects flocculation on the contrary.
  • Such a resin type dispersant may be a commercially available one and Solsperse 24000 and Solsperse 20000 (manufactured by Zeneca K.K.) and Disperbyk-160, Disperbyk-161, Disperbyk-162, Disperbyk-163 and Disperbyk-182 (manufactured by BYK-CHEMIE) may be exemplified.
  • an anionic, nonionic, cationic or amphoteric surfactant is preferably used.
  • anionic surfactants may include a fatty acid salt, alkyl sulfate, alkylaryl sulfonate, alkylnaphthalene sulfonate, dialkyl sulfonate, dialkylsulfosuccinate, alkyldiaryl ether disulfonate, alkyl phosphate, polyoxyethylenealkyl ether sulfate, polyoxyethylenealkylaryl ether sulfate, naphthalenesulfonic acid/formalin condensate, polyoxyethylenealkyl phosphate, glycerol borate fatty acid ester and polyoxyethyleneglycerol fatty acid ester.
  • nonionic surfactants may include a polyoxyethylenealkyl ether, polyoxyethylenealkyl aryl ether, polyoxyethyleneoxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylenesorbitan fatty acid ester, polyoxyethylenesorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylenealkylamine and fluorine type or silicon type nonionic surfactants.
  • cationic surfactants examples include alkylamine salts, quaternary ammonium salts, alkylpyridium salts and alkyl imidazolium salts.
  • alkyl betaine alkylamine oxide and phosphatidyl choline and the like may be exemplified.
  • silane type, titanate type and aluminum type coupling agents and chelate type dispersants are preferably used.
  • silane type may include vinyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane. 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane and the like.
  • titanate type may include isopropyltrilsostearoyl titanate, isopropyltris(dioctylpyrophosphate) titanate, isopropyltri(N-aminoethyl-aminoethyl) titanate, tetraoctylbis(ditridecylphosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosph ite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, isopropyltridodecylbenzenesulfonyl titanate and isopropyltricumylphenyl titanate and the like.
  • acetoalkoxyaluminum diisopropylate, ethylacetate aluminum diisopropylate, aluminum tris(ethylacetoacetate) and aluminum tris(acetylacetonate) and the like may be exemplified.
  • the coating composition for coloring glass according to the present invention is produced in the following method. Specifically, a concentrated dispersion of a pigment is formed either by adding a solvent to the organic pigment, pigment dispersant and the organic resin and dispersing the mixture using a sand grinder mill, or by dispersing the above components except for the solvent using a roll mill followed by making the milled product into solid chips. Then, a silicon alkoxide compound or a metal alkoxide compound and additives are compounded in the concentrated dispersion of a pigment. In the above method, the process using a roll mill to form solid chips is desirable because the organic pigment can be decomposed into primary particles by high shearing force and the organic pigment can be prevented from refloculating by the presence of the pigment dispersant.
  • the organic pigment, the organic resin and the amine derivative may be only mixed when they are dispersed using a roll mill. However, if these components have been in a molten state by mixing under heat in advance prior to the dispersion using a roll mill, not only the affinity between the above amine derivative and the organic resin is improved but also the amine derivative is mixed with the organic pigment uniformly and rapidly, improving productivity.
  • the amount of the pigment dispersant is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the organic pigment.
  • the amount is less than 0.1 parts by weight, no effect is obtained. Even if the pigment dispersion is used in an amount exceeding 30 parts by weight, an effect enough for the amount to be used is not obtained.
  • the coating composition for coloring glass according to the present invention contains a polymerizable organic group-containing alkoxysilane compound.
  • Examples of the polymerizable organic group-containing alkoxysilane compound include compounds represented by the following general formula (6).
  • the compound represented by the general formula (6) is alkoxysilane compounds having the polymerizable organic group R 4 .
  • the polymerizable organic groups are organic groups having an unsaturated double bond or a ring-openable cyclic group and properties of repeating the cleavage of this bond or group and addition and of repeating the addition polymerization.
  • Examples of such a polymerizable organic group may include vinyl groups, 2-propenyl groups, isopropenyl groups, acryloyl groups, methacryloyl groups and ⁇ -methacryloxypropyl groups as the groups having a polymerizable unsaturated double bond and cyclic ether groups, especially, cyclic monoether groups, lactone groups, lactam groups, acid anhydrides and isocyanate groups (and hydroxyl groups) as the groups having a ring-openable cyclic group.
  • vinyl groups or ⁇ -methacryloxypropyl groups are preferable.
  • the coating composition of the present invention may be dissolved or dispersed in a proper solvent.
  • the solvent is selected according to the type of compound and type of pigment to be used or dispersion condition. Generally, ethanol, propanol and butanol are exemplified as the solvent.
  • butanol is preferable in view of the dispersibility of a pigment and ethanol is preferable in the case of making a glassy coating of frost style.
  • the ratio of the silicon alkoxy compound or the metal alkoxy compound to the polymerizable organic group-containing alkoxysilane compound is preferably 15-80 mol%/85-20 mol%.
  • a silicon alkoxide compound or metal alkoxide compound modified by an organic functional group and/or an organic resin may be used. This can make the film thickness of the coating thick, impart flexibility and various resistances to a thin film of a glass gel and improve the storage stability of the coating composition.
  • materials used in such a modification include a silane coupling agent, acrylic resin and the like, polyester resin and epoxy resin. The modification can be attained by condensation-reacting each of these compounds with a silicon or metal alkoxide compound by using a known method.
  • Examples of a solvent used in the above reaction may include almost all alcohols such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, methoxyethanol, ethoxyethanol and propoxyethanol. Also, an organic acid, inorganic acid, amine, coupling agent or the like may be used as a catalyst.
  • organic resin used in the present invention is compatible with the metal alkoxide compound and has the ability of dispersing a pigment.
  • the organic alkoxide compound those having a specific polar group are desirable.
  • an -OH group, -COOH group or -NCO group is preferred.
  • an acrylic resin, polyvinylacetal resin, cellulose resin or urethane resin is preferable as the organic resin in view of the compatibility with a solution of the metal alkoxide compound and the dispersibility of the organic pigment.
  • the molecular weight of the organic resin is preferably 500-100,000 and more preferably 1,000-50,000 in terms of number average.
  • the proportion of the organic resin used in the present invention is 0.1 to 150 parts by weight based on 100 parts by weight of the organic pigment. When the proportion is less than 0.1 parts by weight, no effect is obtained whereas when the proportion exceeds 150 parts by weight, the strength of the thin film is reduced.
  • An organic UV-ray absorber in the present invention is used for the purpose of not only improving the anti-UV-ray characteristics of the organic pigment but also preventing the decomposition of a dye caused by UV-rays when a glass substrate is coated with the coating composition. No particular restriction is imposed on the structure of the absorber.
  • the organic UV-ray absorber concretely a benzotriazole type and benzophenone type are exemplified.
  • benzotriazole type UV-ray absorber may include 2-(2-hydroxyphenyl-3,5-di-t-butylphenyl)benzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)benzotriazole, 2-hydroxyphenyl-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-t-butylphenyl)-5-chlorobenzotriazole, 2- ⁇ 2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-m ethylphenyl)benzotriazole and 2-(2-hydroxy-3,5-dinonylphenyl)benzotriazole and the like.
  • Examples of the benzophenone type UV-ray absorber may include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and 2-hydroxy-4-methoxy-5-sulfobenzone and the like.
  • the organic type UV-light absorber When the organic type UV-light absorber is used in the present invention, its amount is 0.01 to 5 parts by weight based on 100 parts by weight of a coating solution. If the amount is less than 0.01 parts by weight, no effect is obtained. Even if the organic type UV-light absorber is used in amount exceeding 5 parts by weight, not only an effect enough for the amount to be used is not obtained but also this has such an adverse effect that the absorber elutes from the thin film depending upon the condition.
  • the ratio of the amount of total solids (the organic pigment, pigment dispersant, metal alkoxide compound, organic resin and organic type UV-light absorber) to the total amount of the coating solution is preferably 0.1 to 50% by weight.
  • the ratio is less than 0.1% by weight, no practical film thickness is obtained whereas when the ratio exceeds 50% by weight, a problem concerning the stability of the coating solution is posed.
  • additives may be added as far as the object of the present invention is not impaired.
  • the above other additives include, for example, a cross-linking agent. hydrolysis-preventing agent and viscosity regulator and the like.
  • the coating composition for coloring glass according to the present invention may comprise a friction resistance-reducing agent which reduces friction resistance, especially sliding friction, of the formed coating.
  • a friction resistance-reducing agent which reduces friction resistance, especially sliding friction, of the formed coating.
  • the surface of the cured coating becomes smooth and the hardness of the coating is properly controlled.
  • any one of those which don't adversely affect the effect of the present invention may be used.
  • the friction resistance-reducing agent are modified polysiloxane types, more specifically, S030 (trademark, manufactured by Defra in Germany).
  • the glass substrate is coated with the coating liquid composition of the present invention by using a coating apparatus such as a spin coater, roll coater, dip coater, foil coater or bar coater such that the film thickness after being baked is 0.1 to 5 ⁇ m and more preferably 0.5 to 3 ⁇ m.
  • a coating apparatus such as a spin coater, roll coater, dip coater, foil coater or bar coater such that the film thickness after being baked is 0.1 to 5 ⁇ m and more preferably 0.5 to 3 ⁇ m.
  • the film thickness is less than 0.1 ⁇ m, the tinting strength is insufficient whereas when the film thickness exceeds 5 ⁇ m, there is the case where cracks, white turbidity and color spots and the like are caused.
  • the thin film of colored glass gel which is formed on the surface of a glass substrate has effects of improving the abrasion resistance and impact resistance of the glass substrate itself by preventing the abrasion of the glass substrate itself.
  • the thickness is less than 0.1 ⁇ m, such an effect cannot be largely expected.
  • the coating is dried and baked, after it is applied, to form a thin film of colored glass gel on the surface of the glass substrate.
  • the baking temperature is preferably 300°C or less in consideration of the decomposition of the organic pigment and organic dye derivative.
  • the thin film of colored glass gel may be formed by a method other than the above method.
  • light is applied to a coating agent containing a photopolymerization initiator to cause a polymerization reaction thereby curing the coating.
  • the applied light is usually visible light or ultraviolet light and preferably ultraviolet light.
  • Each light source of these lights is optional and may be a mercury lamp, xenon discharge tube, hydrogen discharge tube, black light lamp, various laser light sources or like light sources.
  • the coating can be cured by only one of irradiation with light and heating treatment, it is preferable to combine the both to shorten the time required for heat treatment and to develop higher hardness.
  • Irgazin yellow 5GT manufactured by Ciba-Geigy, C.I. Pigment Yellow 129
  • a polyvinylacetal resin 78.2 parts of 1-butanol
  • a pigment dispersant represented by the structural formula described below
  • 16.7 Parts of the resulting yellow dispersion composition was mixed with 6.5 parts of tetraethoxysilane, 12 parts of water, 1.0 part of nitric acid, 2.0 parts of methanol, 18.0 parts of ethanol, 2.0 parts of 2-propanol and 52.6 parts of 1-butanol in a mixer to obtain a yellow coating composition.
  • the transparency of the coating composition of the present invention when it was made into a thin film is shown using the haze factor. From the fact that each thin film formed using the coating compositions has a low haze factor as shown in Table 2, it is understood that the thin film according to the present invention has sufficient transparency.
  • Each coating composition was dripped on a 50-mm-long, 50-mm-wide and 1.7-mm-thick soda glass and thereafter an excess coating composition was splashed away using a spin coater. Then the soda glass was allowed to stand for 10 minutes and then heated at 200°C for 20 minutes to decrease the film thickness to about 1.5 mm thereby forming test specimens for measuring the haze factor.

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EP00108471A 1999-04-19 2000-04-18 Composition de revêtement pour la coloration de verre Withdrawn EP1052230A1 (fr)

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JP11025399 1999-04-19
JP11110253A JP2000303025A (ja) 1999-04-19 1999-04-19 ガラス着色用コーティング組成物

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1329433A1 (fr) * 2001-10-24 2003-07-23 Centro De Investigaciones Energeticas Medioambientales Y Tecnologicas (C.I.E.M.A.T.) Procédé sol-gel de production de matériau de revêtement poreux par des composés de départ fabriqués par des réactions polymériques
WO2004044487A3 (fr) * 2002-11-14 2005-03-17 Koninkl Philips Electronics Nv Substrat transmettant la lumiere dote d'un revetement absorbant la lumiere, et procede de preparation d'un revetement absorbant la lumiere
WO2012166221A1 (fr) * 2011-02-24 2012-12-06 Owens-Brockway Glass Container Inc. Récipients en verre revêtus d'un sol-gel hybride
EP2762458A1 (fr) * 2013-02-05 2014-08-06 Heinz-Glas Group Holding HGGH GmbH & Co. KGaA Système de scellement et agent de revêtement pour un système de scellement
KR101502334B1 (ko) * 2013-06-20 2015-03-13 에스케이씨 주식회사 내수성이 향상된 합지 유리용 필름
WO2017203180A1 (fr) * 2016-05-25 2017-11-30 Glass Surface Technology Procede de fabrication d'une couche ou d'un motif de revetement de la face interne d'un recipient et recipient obtenu avec un tel procede

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002167237A (ja) * 2000-09-19 2002-06-11 Dainippon Ink & Chem Inc 着色塗装物
JP4671491B2 (ja) * 2000-11-24 2011-04-20 石原薬品株式会社 着色透明被膜形成組成物
KR100671936B1 (ko) 2005-02-17 2007-01-19 한수일 열가소성수지 채색코팅면을 갖는 반투광성 유리타일의 제조방법 및 유리타일
KR101202364B1 (ko) 2009-08-28 2012-11-16 순일산업 주식회사 솔-젤 기술을 이용한 칼라 코팅 유리타일 및 그의 제조방법
CN103287018B (zh) * 2012-03-01 2016-04-06 株式会社神户制钢所 着色树脂涂装金属板
KR101472487B1 (ko) 2013-10-17 2014-12-16 주식회사 딥스 유리 인쇄용 잉크 조성물과 이를 이용한 장식용 유리 및 그 제조방법

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US5232781A (en) * 1989-04-01 1993-08-03 Nippon Sheet Glass Co., Ltd. Method for manufacturing layer-built material with silicon dioxide film containing organic colorant and the layer-built material manufactured thereby
JPH09239311A (ja) * 1996-03-06 1997-09-16 Asahi Beer Packs:Kk 透明カレットとしてリサイクルできるガラスびん用着色コーティング組成物
US5667888A (en) * 1990-04-18 1997-09-16 Matsushita Electric Industrial Co., Ltd. Color filters and methods of manufacturing the same
EP0893737A2 (fr) * 1997-07-24 1999-01-27 JSR Corporation Composition sensible aux radiations
EP0955275A1 (fr) * 1998-04-27 1999-11-10 Toyo Ink Manufacturing Co., Ltd. Composition de revêtement pour la coloration de verre, méthode de sa production et son utilisation

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JPH01275448A (ja) * 1988-04-25 1989-11-06 Unie-Ku T-Pu:Kk ステンドグラスおよびその製造方法
US5232781A (en) * 1989-04-01 1993-08-03 Nippon Sheet Glass Co., Ltd. Method for manufacturing layer-built material with silicon dioxide film containing organic colorant and the layer-built material manufactured thereby
US5667888A (en) * 1990-04-18 1997-09-16 Matsushita Electric Industrial Co., Ltd. Color filters and methods of manufacturing the same
JPH09239311A (ja) * 1996-03-06 1997-09-16 Asahi Beer Packs:Kk 透明カレットとしてリサイクルできるガラスびん用着色コーティング組成物
EP0893737A2 (fr) * 1997-07-24 1999-01-27 JSR Corporation Composition sensible aux radiations
EP0955275A1 (fr) * 1998-04-27 1999-11-10 Toyo Ink Manufacturing Co., Ltd. Composition de revêtement pour la coloration de verre, méthode de sa production et son utilisation

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1329433A1 (fr) * 2001-10-24 2003-07-23 Centro De Investigaciones Energeticas Medioambientales Y Tecnologicas (C.I.E.M.A.T.) Procédé sol-gel de production de matériau de revêtement poreux par des composés de départ fabriqués par des réactions polymériques
WO2004044487A3 (fr) * 2002-11-14 2005-03-17 Koninkl Philips Electronics Nv Substrat transmettant la lumiere dote d'un revetement absorbant la lumiere, et procede de preparation d'un revetement absorbant la lumiere
WO2012166221A1 (fr) * 2011-02-24 2012-12-06 Owens-Brockway Glass Container Inc. Récipients en verre revêtus d'un sol-gel hybride
US10450221B2 (en) 2011-02-24 2019-10-22 Owens-Brockway Glass Container Inc. Hybrid sol-gel coated glass containers
EP2762458A1 (fr) * 2013-02-05 2014-08-06 Heinz-Glas Group Holding HGGH GmbH & Co. KGaA Système de scellement et agent de revêtement pour un système de scellement
KR101502334B1 (ko) * 2013-06-20 2015-03-13 에스케이씨 주식회사 내수성이 향상된 합지 유리용 필름
WO2017203180A1 (fr) * 2016-05-25 2017-11-30 Glass Surface Technology Procede de fabrication d'une couche ou d'un motif de revetement de la face interne d'un recipient et recipient obtenu avec un tel procede
FR3051691A1 (fr) * 2016-05-25 2017-12-01 Glass Surface Tech Procede de fabrication d'une couche ou d'un motif de revetement de la face interne d'un recipient et recipient obtenu avec un tel procede

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